Aminotriazine-aldehyde-halogenated acetone condensation product



Patented Aug. 24, 1943 ALD HYDE HALOGEN- AIWINOTRIAZINE E ATED ACETONECONDENSATION PBOD- UCT Gaetano F. DAieiio, mascara, General ElectricCompany,

New York No Drawing.

Mass. assignor to a corporation of Application January 15, 1941,

Serial No. 374,561

20 Claims.

This invention relates to new condensation products and to methods ofmaking the same.

The invention is concerned more particularly with self-curingaminoplasts, by which are meant heat-convertible resinous condensationproducts prepared from amino or amido compounds and 3 having thecharacteristic property of curing under heat'or under heat and pressureto the insoluble, infu'sible state without the addition of a curingaccelerator or catalyst.

This applicationpis' a continuation-in-part of my co-pending applicationSerial No. 289,276, filed August 9, 1939, now Patent No. 2,323,898,issuedJuly 13, 1943, and assigned to the same assignee as the presentinvention. In that application I disclosed and claimed new and usefulcompositions of matter comprising the condensation product of a mixturecomprising (that is,

of ingredients comprising) a urea, specifically the compoundcorresponding .to. the formula CO(NH2) 2, an aliphatic aldehyde, e. g.,formaldehyde, and a halogenated ketone, specifically a halogenatedacetone. I also disclosed inthat application that, instead of a urea, Imay use a triazine derivative. The present invention is directed to newand useful condensation products of ingredients comprising anaminotriazine (amidogentriazine) an aldehyde, for example formaldehydeor other active methylene-containing body, and a halogenated ketone ofthe kind above mentioned.

In the production of aminoplasts it has heretofore been common practicein coverting such materials to the=insoluble, infusible state toincorporate into the condensation product or into the moldingcomposition a latent or an active (direct) curing catalyst. As pointedout more particularly hereafter, this technique and the final productshave not been wholly satisfactory.

I have-discovered that self-curing aminoplasts can be produced bycondensing an aminotriazine (that is, an aldehyde-reactableaminotriazine),

erty of the product is imparted thereto by creating a resin moleculehaving this inherent characteristic. This is a discovery of greatpractical significance. duction of molding compositions of uniformcuring characteristics, which compositions yield molded articles freefrom imperfections, such as blisters, discolorations, etc. Suchimperfections are due usually to localized curing that often occurs inresinous materials of the admixed catalyst type. As the value of themolded article, especially light-colored articles, is materiallyinfluenced by its appearance, it is clear that the discovery of an meansfor decreasing or eliminating entirely the production of imperfectarticles which must be scrapped or sold at reduced price is ofconsiderable commercial importance.

The resin syrups and molding compositions of this invention may be toredfor long periods of time without material alteration. In marked contrastthe prior heat-convertible aminoplasts of the aminotriazine type (thatis, condensation products of aminotriazines and aldehydes, e. g.,formaldehyde or other active methylene-containing bodies), moreparticularly those containing direct or active curing catalysts such asacids, for example hydrochloric, ethyl sulfuric, phthalic,

chloroacetic, phosphoric, etc., lacked time or, storage stability. Thisnecessitated early use of;

the material afterincorporating the catalyst.

Further, the molding compositions of thisinvention cure rapidly underheat or under heat an aldehyde or an aldehyde-addition product,

and pressure and have good plastic flow during molding. Hence moldedarticles of even the most complicated designs can be produced rapidlyand economically. The cured products have good light stability,excellent water resistance and surface finish and, in general, meet thestrength, hardness and other requirements of the particular serviceapplication.

In carrying the present invention into effect the condensation reactionbetween the components preferably is started under neutral or alkalineconditions. Neutral conditions may be established by neutralizing ,(ifnecessary) either i the mixed components or the individual component orcomponents prior to admixture. Any substance yielding an alkalineaqueoussolution may be used in obtaining alkaline conditions for the initialcondensation reaction. In some cases it may be desirable, in order morequickly toinitiate reaction between the starting materials, to add asmall amount of a suitableorganic or inorganic acid. Thereafter thesolution istreated to eliminate acidic conditions due to acid or Itmakes possible the prov salts. That is, the mass is neutralized or imade alkaline by adding an alkaline substance. The reaction is thencaused to proceed further to produce the self-curing aminoplasts of thisinvention.

In obtaining the neutral, alkaline or acid con ditions above described,I may use, for example, ammonia, sodium hydroxide or carbonate, calciumhydroxide, methyl amine, diethyl amine, triisopropyl amine, ethanolamines, tri-isopropanol amine, etc., mixtures of such alkalinesubstances, inorganic or organic acids such as hydrochloric, sulfuric,phosphoric, acetic, acrylic, crotonic, malonic, etc., or acid salts suchas sodium acid sulfate, monosodium phosphate, etc., or mixtures ofacids, of acid salts, or of acids and acid salts.

Various ways may be employed for effecting initial reaction between thecomponents. For example, I may first mix all the reactants and effectcondensation between the mixed reactants in the presence or absence ofaddition agents, as for instance, condensation catalysts, fillers,plasticizers, other natural or synthetic resinous bodies, solvents ordiluents, etc. Alternatively, I may add the halogenated ketone to apartial condensation product of an aminotriazine and an aldehyde andeffect further condensation between the components. In producing such apartial condensation product I prefer to cause the condensation reactionbetween the aminotriazine and the aldehyde to take place in th presenceof a primary condensation catalyst and a secondary condensationcatalyst. The primary catalyst advantageously is a member of the classconsisting of l 1) nitrogen-containing basic tertiary compounds that arealdehyde-non-reactable, e. g., tertiary amines such as trialkyl (forexample, trlmethyl, triethyl, etc.) amines, triaryl (for example,triphenyl, etc.) amines, etc., and (2) nitrogen-containing basiccompounds that are aldehyde-reactable, for instance ammonia, primaryamines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e.g., dipropyl amine, dibutyl amine, etc.). The secondary condensationcatalyst, which ordinarily is used in an amount less than the amount ofprimary catalyst, should be a fixed alkali, for instance a carbonate,cyanide or hydroxide of an alkali metal (e. g., sodium, potassium,lithium, etc.).

Another method of effecting reaction between the ingredients comprisesfirst condensing the halogenated ketone with an aldehyde, e. g.,formaldehyde or other active methylene-containing body, adding theresulting product to a partial condensation product of an aminotriazineand an aldehyde and then causing the reaction to proceed further. Or, Imay condense or partially condense the halogenated ketone with 9. molexcess of an aldehyde, add an aminotriazine-to this condensation productand effect further reaction be tween the components. Or, I may partiallycondense the halogenated ketone with an excess of an aminotriazine andadd to this condensation product one mol of an aldehyde for each molexcess of aminotriazine present and efiect further condensation. Stillother ways may be employed in combining the components and in producingthe unmodified and modified condensation products of this invention, aswill be readily understood by those skilled in the art as thedescription of the invention proceeds. These condensation reactions mayproceed under a wide variety of time, temperature and pressureconditions. The temperature of reaction may vary from room temperatureto the reflux temperature of the reactants at reduced, atmospheric orsuperatmospheric pressures.

The products obtained as described above properly may be designated asintermediate condensation products. They are heat-convertible resinousbodies which alone or mixed with fillers, pigments, dyes, lubricants,plasticizers, etc., may be used, for example, as molding compositions.The modflied and unmodified resinous masses are selfconvertible underheat or under heat and pressure to the insoluble, infusible state.

Depending upon the particular reactants employed and the particularconditions of reaction, these intermediate condensation products varyfrom clear, colorless, syrupy, water-soluble liqulds to viscous, milkydispersions and gel-like masses of decreased solubility in ordinarysolvents, such as alcohol, glycol, glycerine, water, etc. These liquidintermediate condensation products may be concentrated or dilutedfurther by the removal or addition of volatile solvents to form liquidcoating compositions of adjusted viscosity and concentration. The liquidcompositions may be used, for instance, as surface-coating materials, inthe production of paints, varnishes, lacquers, enamels, etc., forgeneral adhesive applications, in producing laminated articles and fornumerous other purposes. The liquid intermediate condensation productsalso may be used directly as casting resins. Those intermediate productsof a gel-like nature may be dried and granulated to form clear,unfilled,heatconvertible resins.

In order that those skilled in the art better may understand how thisinvention may be carried into effect, the following examples are givenby Way 01' illustration. All parts are by weight.

Example 1 Parts Melamine 63.0 Aqueous solution of formaldehyde(approximately 37.1% HCHO) 140.0 Aqueous ammonia (28% NHs) 3.0 Sodiumhydroxide in 15 parts water 0.06 Chloroacetone 0.5

All of the above components with the exception of the chloroacetone weremixed and heated under reflux at the boiling temperature of the mass for10 minutes. The stated amountof chloroacetone was now added and heatingunder reflux was continued for 5 minutes to cause the chloroacetone tointercondense with the melamineformaldehyde partial condensationproduct. The hot resinous syrup was mixed with 67 parts alpha cellulosein flock form and 0.4 part of a mold lubricant, specifically zincstearate, to form a molding (moldable) compound. 'Ihe wet compound wasdried at 67 C. for 2 hours. The dried compound was molded for 3 minutesat C. under a pressure of 2,000 pounds per square inch. The moldedpieces could be pulled hot from the mold without distortion. They werehard and well cured throughout and had excellent gloss, color andsurface appearance.

Example 2 Example 3 Parts Melamine 31.5 Urea 15.0 Aqueous solution offormaldehyde (approximately 37.1% HCHO) 100.0 Aqueous ammonia (28% NHa)3.0 Sodium hydroxide in 3 parts water 0.06 Alpha, alpha primedichloroacetone 0.114

All of the above components with the exception of the alpha, alpha primedichloroacetone were heated together under reflux at boiling temperaturefor 30 minutes. The chlorinated acetone was now added andthe mixture washeated to boiling temperature. The hot resinous syrup was mixed with47.5 parts alpha cellulose in flock form and 0.4 part zinc stearate toform a molding compound. The wet compound was dried at 63 C. for 3 hoursand then at 75 C. for 1 hours. The dried compound was molded for 2minutes at 130 C. under a pressure of 2,000 pounds per square inch. Themolded pieces could be pulled hot from the mold without distortion. Theywere well cured throughout and of good surface appearance.

' Example 4 1 Parts Melamine 31.5 Thiourea 19.0

Aqueous solution of formaldehyde (approximately 37.1% I-ICHO) 100.0Aqueous ammonia (28% NHa) 3.0 Sodium hydroxide in 3 parts water 0.06Alpha, alpha prime diohloroacetone 0.12

The same procedurewas followed as described under Example 3 with theexception that the initial components (in the absence of the chlorinatedacetone) were heated under reflux for 15 minutes to form themelamine-thiourea-formaldehyde partial condensation product. Afteradding the alpha, alpha prime diohloroacetone and bringing the reactionmass to boiling temperature, the resulting syrup was mixed with 49vparts alpha cellulose in flock form and 0.4

part zinc stearate to form a molding composition. The wet compound wasair dried at room temperature until sufiiciently freed of moisture forproper molding. Well-cured molded articles were obtained when the driedcompound was molded at 130 C. undera pressure of 2,000 pounds per squareinch. The molded pieces had excellent resistance to water.

- Example 5 Parts Melamine -1 47.2.5 Dicyandiamide 10.5 Aqueous solutionof formaldehyde (approximately 37.1% HCHO) 120.0 Aqueous ammonia (28%NI-Is) 3.0 Sodium hydroxide in 3 parts water Alpha, alpha primedichloroacetone All of the above components with the exception of thealpha, alpha prime dichloroacetone were droxy-l,3,5-triazine,

pressure of 2,000 pounds per square inch. The

molded pieces were well cured throughout,

It will be understood, 01. course, that the haloeenated ketonesmentioned in the above examples are only by way oi. illustration andthat various other halogenated ketones, more par- I self-curing resinsare obtained. When low-b0iling halogenated ketones are used in this way,the halogenated ketone tends to distill of! before the condensationreaction is complete. In practicing my invention I prefer, because ofeconomic factors, to use in large part low-boiling halogenated ketones,such as chloroacetone. Therefore it is desirable that these compounds becondensed into the mass by heating under reflux.

It also will be understood that in each of the specific halogenatedketones above mentioned the particular halogen shown in any specificformula may be replaced by some other halogen, care being taken in thechoice of the halogen in the light of the properties desired in thefinal product. For example, when light-colored molded articles aredesired, the use of iodoketones should be avoided and when theheatcurable resins are to be used in the production of moldingcompositions, the fiuoroketones prelerably are avoided.

Where a plurality of halogen atoms are present in the ketone molecule,these may be the same or different. For example, one halogen in themolecule may be chlorine and another bromine. In this way it is possibleto obtain a heat-convertible resin of self-curing characteristics,andother properties best adapted to meet a particular molding problem andservice application of the finished article.

Likewise, it also will be understood that the aminotriazine named in theabove examples (melamine) is by way of illustration and that any otheraldehyde-reactable aminotriazine (amidogentriazine) may be employed. Iprefer to use triazines containing either at least one unsubstitutedamidogen (NH"a)' group or a plurality of partly substituted amidogengroups. Examples of such triazines which may be used in producing thenew synthetic materialsof this invention are ammeline, ammelide,formoguanamine, 2-amino-1,3,5-triazine and its substitution products;derivatives of melamine, e. g., 2,4,6- trihydrazino 1,3,5 triazine,melam, melon, 2,4,6-triethyltriamino 1,3,5 trazine, 2,4,6triphenyltriamino- 1,3,5-triazine, etc.; nuclearly substitutedaminotriazines, e. g., 1-cyano-2- amino-4,6- -dimethyl-1,3,5-triazine,2-chloro-4,6- diamino-l,3,5-triazine, 6-methyl-2,4 diamino- 1,3,5triazine, 2 alkyl 4 amino 6 hydroxy- 1 .,3,5-triazines (e. g.,2-methyl-4-amino-6-hyetc.), 2-aryl-4-amino-6- hydroxy-l,3,5-triazines(e. g., 2-phenyl-4-amino-S-hydroxy-1,3,5-triazine, etc),2-phenyl-poxy-4,6-diamino-1,3,5-triazine; poly-amino triazines whereinthe hydrogen atoms of one or all of the amino groups are partiallysubstituted by other amino groups, e. g.,2,4-diamino-6-hydrazino-1,3,5-triazine, 2-amino-4,6-dihydrazinq-1,3,5-triazine, 2,4,6-trihydrazino 1,3,5-triazine, eta; poly-aminotriazines wherein the hydrogen atoms of one or all of the amino groupsare partially substituted by other monovalent substituents (e. g.,alkyl, aryl, aralkyl, alkaryl, etc.), for instance2-amino-4,6-diethylamino-1,3,5-tri- ,azine, 4-amino-2,6-diphenylamino1,3,5 triazine, 2-methylamino-4-amino-6-chloro 1,3,5- trlazine, 2,4diamino 6 phenylamino-1,3,5- triazine, symmetrical trialkyl and triarylmelamines; the amidogen 1,2,3-triazines and the amidogen1,2,4-triazines, specifically the amino (-NHz) and the carbamyl (-CONHz)and the thiocarbamyl (-CSNHz) 1,2,3- and 1,2,4-triazines. Additionalexamples of amidogen 1,3,5- triazines are given below:

Other examples of amidogen triazines are the amidogen 1,2,3- and1,2,4-triazines corresponding to the above amidogen 1,3,5-triazines.Additional examples of amidogen triazines which may be used in carryingthe present invention into eilect are given in various copendingapplications of mine, for example application Serial No. 404,661, filedJuly 30, 1941, now Patent No. 2,312,688, issued March 2, 1943, andassigned to the same assignee as this invention. The preferred class oftriazine derivatives used in carrying the present invention into effectare the 2,4,6- amidogen-1,3,5-triazines.

In producing these new condensation products the choice of the aldehydicreactant is dependent largely upon economic considerations and upon theparticular properties desired in the finished product. I prefer to useas the aldehydic reactant formaldehyde or compounds engenderingformaldehyde, e. g., paraformaldehyde, hexamethylene tetramine, etc. Forsome applications I may use, for instance, acetaldehyde,propionaldehyde, butyraldehyde, acrolein, methacrolein, crotonaldehyde,benzaldehyde, i'urfural, etc., mixtures thereof, or mixtures offormaldehyde (or compounds engendering formaldehyde) with suchaldehydes. Examples of aldehyde-addition products that may be usedinstead of the aldehydes themselves are the formaldehyde-additionproducts of urea, thiourea and iminourea and of substituted ureas,thioureas and iminoureas (e. g., monoand di-methylol ureas andthioureas) and the formaldehyde-addition products of the aminotriazines(e. g., mono-, di-, tri-, tetra-, pentaand hexa-methylol melamines).Mixtures of aldehydes and aldehydeaddition products may be employed, e.g., mixtures of formaldehyde and methylol compounds such, for instance,as dimethylol urea and trimethylol melamine.

As shown by Examples 3, 4 and 5, a part of the aminotriazine reactantmay be replaced, if desired, by a urea, e. g., urea itself, thiourea,iminourea and their aldehyde-reactable substitution products, numerousexamples of which latter are given in my 'copending application SerialNo. 289,276. I may use either a single or a plurality of halogenatedacetones with the aminotriazine reactant or with the aminotriazine andurea reactants. Various aminodiazines or aminodiazoles also may be usedin place of a part or the aminotriazine reactant.

The ratio of the reactants to each other may be considerably varied,but, in general, it is desirable to useat least one mol of an aldehyde,e. g., formaldehyde or other active methylenecontaining body, for eachmol of mixed (total) ketone and aminotriazine, or at least one mol ofmixed (total) aldehyde and ketone for each mol of aminotriazine. Inproducing the heatconvertible resinous condensation products of thisinvention, the proportion of halogenated ketone in all cases is at leastsufiicient to impart selfcuring characteristics to the resin. Ordinarilynot exceeding substantially mol halogenated ketone is used for each molof aminotriazine. No advantage ordinarily accrues from using an amountof halogenated ketone above the minimum required to secure the desiredcuring rate.

Further, the use of higher amounts of halogenated ketone is undesirablefor most molding applications because of the greater difllculty inobtaining molded articles of suitable hardness,

but may not be objectionable for other applications of the material.Also, in some cases, particularly where high genated ketones, as forexample alpha halogenated methyl octadecyl ketone, are used, thehalogenated ketone exceeds on a weight basis the aminotriazine portionof the molecule. Consequently, in such cases the inherentcharacteristics (for example, waxy nature) of the high molecular weighthalogenated ketone predominate in the resin molecule. This may beobjectionable in some applications of the molded part, for example whereresistance to the ordinary organic solvents is required.

From the foregoing it will be seen that the particular mol ratio ofhalogenated ketone to the other components is dependent somewhat uponthe inherent characteristics of the halogenated ketone and the curingcharacteristics and other properties desired in the heat-curable andheatcured resinous condensation products. For molding applications theratio of the aldehydic reactant to the aminotriazine may be considerablyvaried, but generally will be within the range of 1% to 3% molsaldehyde, e. g., formaldehyde, for each mol of aminotriazine. Noparticular advantage ordinarily accrues from the use of higher amountsof aldehyde. Taking melamine (an aminotriazine containing threeunsubstituted amidogen groups) as illustrative of the aminotriazine,particularly good results are obtained with approximately three molsaldehyde, e. g., formaldehyde, for each moi melamine. If theaminotriazine contains only two unsubstituted molecular weighthaloamidogen groups (or one unsubstituted and two partly substitutedamidogen groups), then one advantageously may use approximately two molsaldehyde for each mol of an aminotriazine. If

-. the aminotriazine contains only one unsubstituted amidogen group (ortwo partly substituted amidogen groups), then no particular advantageusually accrues from using much in excess of one mol aldehyde for eachmol of such an aminotriazine.

The properties of the fundamental resins of this invention may be variedwidely by introducing other modifying bodies before, during or aftereffecting condensation between the primary components. Thus, asmodifying agents I may use, for instance, monohydric alcohols such asethyl, propyl, isopropyl, butyl, ain'yl, etc., alcohols; polyhydricalcohols such as ethylene glycol, diethylene glycol, glycerine,pentaerythritol, etc.; amides such as formamide, acetamide, stearamide,acryloamide, benzamide, toluene sulfonamides, benzene disulfonamides,benzene trisulfonamides, adipic diamide, phthalamide, etc.; amines suchas ethylene diamine, aniline, phenylene diamine, etc.; phenols;aminophenols; ketones other than the hereindescrlbed halogenatedketones; nitriles, e. g., acrylonitrile, methacrylonitrile,succinonitrile, etc.; and others.

The modifying bodies also may take the form of high molecular weightbodies with or without resinous characteristics, for example hydrolyzedwood products, formalized cellulose derivatives, lignin, proteins,protein-aldehyde condensation products, aminodiazineandaminodiazole-aldehyde condensation products, phenol-aldehydecondensation products, urea-aldehyde condensation products,aniline-aldehyde condensation products, furfural condensation products,modifled or unmodified, saturated or unsaturated polyhydricalcohol-polybasic acid condensation products, sulfonamide-aldehyderesins, water-soluble cellulose derivatives, natural gums and resinssuch as shellac, rosin, etc.; polyvinyl compounds such as polyvinylalcohol, polyvinyl acetate, polyvinyl acetals, specifically polyvinylformal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and variousfillers (e.'g., wood flour, lass fibers, asbestos, including defibratedasbestos, mineral wool, mica, cloth cuttings, etc.) may be compoundedwith the resin in accordance with conventional practice to providemolding compositions best fitted to yield molded articles of optimumproperties for the particular service application.

The molding compositions of this invention may be molded into a varietyof shapes under heat and pressure, more particularly at temperatures ofthe order of 100 to 200 C., preferably from 120 to 180 C. Moldingpressures may be varied considerably, but usually are within the rangeof 1,000 to 10,000 pounds per square inch, more particularly from 2,000to 4,000 or 5,000 pounds per square inch.

From the foregoing description it will be seen that the presentinvention provides new and useful compositions of matter comprising acondensation product (in heat-curable or heat-cured state) ofingredients comprising essentially. an aminotriazine (amidogentriazine),e. g., melamine, an aldehyde (including polymeric aldehydes andaldehyde-addition products), e. g., formaldehyde, paraformaldehyde,dimethylol urea, etc., and at least one halogenated acetone. The scopeof the invention also includes method products. For instance. one methodfeature of the invention comprises effecting partial reaction betweeningredients comprising an aminotrlazine, specifically melamine, analdehyde or an aldehyde-addition product, specifically formaldehydeordimethylol urea (or ingredients comprising a urea, specificallyNHaCONHa, an aminotriazine and. an aldehyde or an aldehyde-additionproduct) in the presence of an alkaline condensation catalyst,specifically a condensation catalyst comprising ammonia and a fixedalkali, adding a small amount of one or more of the hereindescribedhalogenated ketones,'e. g., a halogenated acetone such as chloroacetone,to the resulting partial condensation product and causing thehalogenated acetone to intercondense with the said partial condensationproduct. My invention also provides thermosetting (heat-hardenable)molding compositions comprising a filler, e. g., a cellulosic filler,and a heat-curable condensation product of this invention, e. g., aheat-hardenable (heat-curable) condensation product of ingredientscomprising melamine (or urea and melamine), formaldehyde or compoundsengendering formaldehyde and a halogenated acetone, specifically achlorinated acetone (mono-, dior tri-chloroacetone as well as moldedarticles of manufacture comprising the heat-set molding compositions.

The modifiedand unmodified resinous compositions of this invention havea wide variety of uses. For example, in addition to their use in theproduction of molding compositions, they may be used as laminatingvarnishes in the production of laminated articles wherein sheetmaterials, e. g., paper, cloth, sheet asbestos, etc., are coated andimpregnated with the resin, superimposed, and thereafter united underheat and pressure. They also may be used in the production of wire orbaking enamels, ior bonding or cementing together mica flakes to form alaminated mica article, for bonding together abrasive grains in theproduction of resin-bonded abrasive articles such, for instance, asgrindstones, sandpapers, especially those intended for wet-sandingoperations, in the manufacture of electrical resistors, etc. They alsomay be used as fire retardants and sizings, for instance in thetreatment of cotton, linen and other cellulosic materials. They also maybe used as impregnants for electrical coils. The cured resinous productshave a high dielectric strength and outstanding resistance to heat,moisture and arcing. Hence they are especially adapt d for use inelectrically insulating applications wherein solid insulation possessinthese characteristics is particularly desirable.

What .I. claim as new and desire to secure by Letters Patent or theUnited States is:

i. A. composition of matter comprising the condensation product oringredients comprising essentially an 'aminotriazine, an aldehyde and ahalogenated acetone.

2. A composition of matter comprising an alcohoi-modmeu condensationproduct of ingredients comprising an aminotriazine, an aldehyde and atleast one halogenated acetone.

3. A heat-curable resinous condensation product of ingredientscomprising essentially an aminotriazine, formaldehyde and at least onehalogenated acetone.

4. A. product comprising the heat-cured resinous condensation product ofclaim 3.

5. A composition comprising a condensation features for the productionor such condensation Product Of ingredients comprising an aminotri- "-ihmsrtion of claim 6.

azine, a urea containing a methylol radical, and at least onehalogenated acetone.

6. A heat-curable resinous composition comprising a soluble, fusiblecondensation product of ingredients comprising the following componentsin the stated moi ratios: 1 mol of an aminotriazine, from 1% to 3% molsformaldehyde and not exceeding substantially mol of a halogenatedacetone.

7. A product comprising the cured resinous 8. A composition as in claim1 wherein the aminotriazine is melamine and the aldehyde isformaldehyde.

9. A heat-curable resinous condensation product of ingredientscomprising urea, melamine, formaldehyde and a, halogenated acetone.

10. A product comprising the heat-cured resinous condensation product ofclaim 9.

11. A composition comprising the product of reaction of (1) a partialcondensation product obtained by reaction, while admixed with analkaline substance, of ingredients comprising an aminotriazine andformaldehyde and (2) a halogenated acetone.

12. A composition comprising the reaction product of ingredientscomprising an aminotriazine, an aldehyde and a chlorinated acetone.

13. A composition comprising the product of reaction of ingredientscomprising an aminotri- 'azine, formaldehyde and a chlorinated acetone.

14. A composition comprising the product of reaction of ingredientscomprising an aminotriazine, dimethylol urea and a chlorinated acetone.

15. A composition comprising the product of reaction of ingredientscomprising .urea, melamine, formaldehyde and a chlorinated acetone.

16. A thermosetting molding composition comprising a, filler and aheat-hardenable condensation product of ingredients comprising anaminotriazine, formaldehyde and a halogenated acetone.

17. A heathardenable molding composition comprising a cellulosic fillerand a heat-curable condensation product of ingredients comprisingmelamine, formaldehyde and a chlorinated acetone 18. A productcomprising the heat-hardened molding composition of claim 17.

19. The method of preparing new condensation products which comprisesfiecting reaction between ingredients comprising essentially anaminotriazine, an aldehyde and a halogenated acetone.

20. The method which comprises effecting partial reaction betweeningredients comprising melamine, urea and formaldehyde in the presenceof a condensation catalyst comprising ammonia and a fixed alkali, addinga small amount of a chlorinated acetone to the resulting partialcondensation product and causing the chlorinated acetone tointercondense with the said partial condensation product.

GAETANO 1 DALELIO.

p CERTIFICATE OF connscnon. Patent No. 2,527,771. 7 7 August 21;, 1915.

GAETANO F. D'AIELIO.

It is hereby certified that error appears in the printed specificationof the above mmhered patent requiring correction as follows: Page 2,second'column, line 9, for "modfiied" .read --modi fied-; pege 5, secondcol-- umn, lines 28 and 29, strike out the words "shown in any specificformula." and insertv instead --specified--; line 61, for "trazine" read--tr1azine--; line 70, after "etc" and before the parenthesis insert aperiod; page 1;, first column, line 27, for "(para-benzamide)" read--(semicarbazido)-; page 5,

first column, line 2.,for 'scryloamide read -acrylemide--; and that thesaid Letters Patent should be reed with this correction therein that thesame may conform to the record of the case in the Patent Office. v Signed and sealed this 2nd day of Novenber, A. D. 1915.

Henry Van Arsdale, (Seal) Acting Commissioner of Patents.

